A heteroaryl sulfonyl(VI) fluoride, 4-chloro-7-fluorosulfonyl-2,1,3-benzoxadiazole, was synthesized from its chloride counterpart (4-chloro-7-chlorosulfonyl-2,1,3-benzoxadiazole) and the X-ray structure analysis of these compounds and the interactions in the solid-state were thoroughly examined. Hirshfeld surface analysis is used to provide a thorough and complete picture of the changes arising from the different halides in the functional groups. Surface analysis reveals that the fluoride does not participate in any hydrogen interactions as opposed to the chloride. However, the fluorine atom is observed to form close interactions with several π bonds. For both moieties, however, the sulfonyl oxygens show comparable interactions with respect to both magnitude and interatomic distances. The Hirshfeld surface analysis is coupled with computational studies to help elucidate the observed interactions that are found from the distinct nitrogen, chlorine, and oxygen atoms present in the molecules, providing new physical insights to the correlation between their structures and properties.